Diazonium compounds



Patented Dec. 3, 1935 UNITED STATES PATENT OFFICE DIAZONIUM COMPOUNDS N Drawing. Application February 9, 1933, Serial No. 656,026. In Germany February 13, 1932 4 Claims.

The present invention relates to new diazonium compounds, more particularly it relates to compounds which may be represented by the general formula:

wherein R stands for the radical of a diazotized non-sulfonated diazotization component suitable for producing azodyestuffs, R stands for an arcmatic radical, for example, for a benzene-, naphthalene-, carbazole-, anthraceneand acenaphthene nucleus and X stands for the radical of a carboxylic acid which is attached with the carbon atom of the CO-group to the N-atom of the NH-group, and wherein R and R may be substituted, for example, by alkyl, alkoxy, halogen, the substituted amino group, such as acylamino and alkylamino or phenylamino, further carboxyl and in the case of R also by the sulfonic acid group.

Our new diazonium compounds are obtainable by diazotizing a highly concentrated aqueous solution of a non-sulfonated diazotization component suitable for producing an azodyestuff in the usual manner, for example, with hydrochloric acid and sodium nitrite, and adding thereto a highly concentrated aqueous solution of an aromatic sulfonic acid substituted at least once by the radical of an acylamino group derived from a carboxylic acid, or of a water-soluble salt, especially an alkali metal salt, thereof, care being taken that the process is performed at low temperatures, say between 0 and 10 C., and that the concentration of the solutions poured together is as high as possible, in order to facilitate the separation of the new diazonium salts formed.

In some cases when the solubility of the new diazonium compound formed is extremely high, a method of their manufacture resides in preparing a highly concentrated solution of the diazonium compound and adding thereto a watersoluble salt of theacylamino-arylsulfonic acid in a finely divided form or the free acid.

The new compounds generally crystallize from their solutions from which they are separated by filtering with suction. They are dried at moderate temperature, say between temperatures of 20-50 C., if desired, with the application of a vacuo, and are obtained in form of stable, yellow to orange, more or less water soluble crystalline substances. They are valuable intermediate products in the manufacture of azodyestuffs, inasmuch as they are soluble in water, yielding diazo solutions which can be coupled in the usual manner with coupling components forming azodyestuffs.

The invention is illustrated by the following examples, without being limited thereto:

Example 1.142,5 parts by weight of 4-chloro- 2-amino-l-methylbenzene are diazotized in a concentrated aqueous solution with hydrochloric acid and 69 parts by weight of sodium nitrite. In this solution there is dissolved at a temperature below 20 C. somewhat more than the calculated quantity of 1-acetylaminobenzene-4-sodium sulfonate; After a short time yellow crys tals separate, and by cooling down to zero the separation can be completed. The crystal magma is centrifuged and the crystals thus obtained are dried at a temperature below 50 C. The dry diazonium salt of the l-acetylaminobenzenel-sulfonic acid which probably corresponds to the following formula:

properties.

Example 2.152 parts by weight of 5-nitro-2- amino-l-methylbenzene are diazotized in a concentrated aqueous solution with hydrochloric acid and 69 parts by weight of sodium nitrite. Into the solution thus obtained there is introduced a concentrated solution of somewhat more than the calculated quantity of 2-acetylaminobenzene-4- sulfonic acid-l-carboxylic acid, whereupon the diazonium salt of the probable formula separates in beautiful crystals. The reaction weight of sodium nitrite and 400 parts by weight of water. The diazo solution is filtered, thereto is added a solution of 950 parts by weight of l-acetylaminobenzene-l-sodium sulfonate in 700 2. The diazonium salts of the general formula:

R-N=N-SO3R'-NHX wherein R stands for the radical of a diazotized parts by weight of water. The mixture solidinon-sulfonated diazotization component of the 5 fies to an intense yellow crystal magma; the benzene or naphthalene series, R stands for a same is cooled to C., while stirring, and radical of the benzene or naphthalene series and filtered with suction. Drying is performed at X stands for the radical of a carboxylic acid which 20-25 C. The diazonium salt of the probable is attached with the carbon atom of the CO- formula group to the N-atom of the NH-group, being gen- 10 erally stable, yellow to orange, crystalline sub- OH; stances, soluble in water, and being valuable intermediate products in the manufacture of dye- OzN N=NOaS-C NH-C 0cn3 stuffs.

3. The diazonium salt of the formula: is a yellow crystalline powder, easily soluble in water. CH3

In the following table there are given the colorations and solubilities of the diazonium salts N=NOaS-C NHCOOH: of some further acylaminoarylsulfonic acids with some diazotized bases. being a stable, yellow, crystalline substance,

Coloration of the diazonium Solubility of the Acidylammoaryl sulfonic acid Diazotized base Salt diazomum salt 1. l-acetylaminobenzene-i-sulfonic acid 5-nitro-2-amino-l-methylbenzene Golden yellow Well soluble.

Do 3-chloro-1-aminobenzene Pale yellow" Very well soluble. Do. 3-nitro-4-arnino-l-methylbenzene Orange Very well soluble.

Z-amino-5-benzoylamino-hydroquinone- Greenish yellow Diflicultly soluble.

diethylether. 2l5-dichloro-aniline Yellow Well soluble. G-chloro-Z-amino-l-methylbenzene Yellow Well soluble. 2. 3-chloro-l-aminobemene White Very well soluble. 3. 4-chloro-2-amino-l-methylbenzene Yellow Very well soluble.

4-nitro-2-amino-1-methylbenzene Yellowish-orange Well soluble. Do 5-nitro-2-an1ino-1-1nethylbenzene Yellowish-orange- Well soluble. 4. l-aceilylaminonaphthalene-5-sulfonic 5-nitro-2ramino-l-methylbenzene Orange Rather soluble.

Do 3-ohloro-l-aminobemene Yellowi h Very well soluble. 5. l-acelaylaminobenzene-ZA-disulfonic 5-nitro-2-amino-l-methylbenzene Yellow Very well soluble.

8C1 6. 2acetylamino-1-methylbenzene-4,5- 4-nitrO-2-81Ilin0-l-methylbenzene Yellow Well soluble.

disulfonic acid 7. Z-afcetylamnonaphthalene-5,7-disul- 4-chloro-2-amino-1-methylhenmne Yellow Verywell soluble.

01110 201 V 8. 2-acet ylamno-l-benzoicacid-4-sul- 5-nitro-2-amino-l-metl1ylbenzene Golden yellow- Well soluble. 40

01110301 9. l-acegylaminoinaphthalene-4,6,8-trirn-toluidine-azo-meta toluidine Brown Rather soluble.

S 01110 8.01 l0.1,? bis 2gwtylaminobenzene-4-sulfon- 4-chloro-2-amino-l-methylhenmm Yellow Well soluble.

10 am V 11. l-acetylamno-2'chlorobenzene-4-sul- 4-chloro-2-amino-l-methylhen ene Yellow Very well soluble.

OHIO 8101 12. l chloroagetylaminobenzene-4- sul- 3-ohloro-l-aminob ens Yellow 4. Very well soluble.

01110 301 13. l -url 0p ionyldaminobenzene 4 4-chloro-2-amino-1-methylbenzene Yellow Very well soluble.

S 011103.01 14. 1 -fbenzoyl;1mino benzene 4 sul- 4-chloro-z-amino-l-methylbenzene Pale yellow Difiiicultly soluble.

01110 301 15. Ethylester oxalylamino benzene 3-chloro-1-aminobenzene White Very well soluble.

4sulfonic acid. 5O 16. 4-sulfophenyl-oxaminic acid 4-nitro-2-arnino-1-methylbenzene Very well soluble. 17.4-sulfophenylurea 4-chloro-2-amino-1-methylbenzene Well soluble. 18. l-solfophenylthiourea 4-chloro-2-arnino-1-methylbenzene Well soluble. 19. Ureagfl-aminobenzenel-sulfonic 4-chloro-2-amino-1-methylbenzene Pale yellow Higher diflicultly $0111- 361 e. 20. 4,4-disu.lfodiphenyloxamide (sodi- 3-chloro-l-aminobenzene Yellow Well soluble.

inn sulionate) We claim: soluble in water, and being a valuable interme- 1. The diazonium salts of the general formula: diate product in the manufacture of dyestuffs.

4. The diazonium salt of the formula: RN=NSO3R'NHX wherein R stands for the radical of a diazotized non-sulfonated diazotization component suitable 0 N O 8 NH 00 OH for producing azodyestuffs, R stands for an 2 a aromatic radical and X stands for the radical of a carboxylic acid which is attached with the carbon being a stable, yellow, crystalline substance, at of the P p t0 the N-atom 0f t soluble in water, and. being a valuable intermeer p, h e generally sta y l w to a g diate product in the manufacture of dyestuffs. crystalline substances soluble in water, and being valuable intermediate products in the manufac- ANTON OSSENBECK.

ture of dyestuifs.

ERNST TIETZE. 

